WO2007111126A1 - Method of substrate treatment, process for producing semiconductor device, substrate treating apparatus, and recording medium - Google Patents

Method of substrate treatment, process for producing semiconductor device, substrate treating apparatus, and recording medium Download PDF

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Publication number
WO2007111126A1
WO2007111126A1 PCT/JP2007/054975 JP2007054975W WO2007111126A1 WO 2007111126 A1 WO2007111126 A1 WO 2007111126A1 JP 2007054975 W JP2007054975 W JP 2007054975W WO 2007111126 A1 WO2007111126 A1 WO 2007111126A1
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Prior art keywords
substrate
organic acid
processing
processed
semiconductor device
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PCT/JP2007/054975
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French (fr)
Japanese (ja)
Inventor
Hidenori Miyoshi
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Tokyo Electron Limited
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Publication date
Application filed by Tokyo Electron Limited filed Critical Tokyo Electron Limited
Priority to CN2007800111178A priority Critical patent/CN101410954B/en
Priority to JP2008507419A priority patent/JPWO2007111126A1/en
Priority to US12/282,963 priority patent/US20090087995A1/en
Publication of WO2007111126A1 publication Critical patent/WO2007111126A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment
    • H01L21/67109—Apparatus for thermal treatment mainly by convection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
    • H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
    • H01L21/76828—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. thermal treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers

Definitions

  • Substrate processing method semiconductor device manufacturing method, substrate processing apparatus, and recording medium
  • the present invention relates to a method for manufacturing a semiconductor device using metal wiring.
  • the formic acid and acetic acid described above are highly corrosive to the metal materials used in the substrate processing apparatus. Therefore, there is a concern that the substrate to be processed may be contaminated with the metal when the substrate is processed. It was.
  • piping for transporting processing gas and raw materials used in a substrate processing apparatus is mostly formed of a metal material such as a stainless alloy.
  • a metal material such as a stainless alloy.
  • formic acid and acetic acid are corrosive to such metal materials.
  • the substrate processing apparatus is contaminated with metal, and therefore the substrate to be processed is contaminated with metal.
  • Patent Document 1 Japanese Patent No. 3373499
  • the present invention provides a novel and useful substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium storing the substrate processing method, which solve the above-described problems. For the purpose.
  • a specific problem of the present invention is to reduce the influence of metal contamination when an oxide film formed on a metal wiring is removed in a semiconductor device manufacturing process.
  • a substrate processing method for a substrate to be processed in which an insulating film and a metal layer are formed, wherein an organic acid ammonium salt is formed on the substrate to be processed A substrate processing method comprising: supplying a vapor of a substance containing at least one of an organic acid amine salt, an organic acid amide, and an organic acid hydrazide and heating the substrate to be processed.
  • a semiconductor device manufacturing method including a metal wiring and an interlayer insulating film, wherein the metal wiring and the interlayer insulating film are formed.
  • a vapor of a substance containing at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is supplied onto the substrate to be processed and the substrate to be processed is heated.
  • the above-described problem is solved by holding a substrate to be processed and heating the substrate to be processed, a processing container having the holding table therein, A substrate processing apparatus comprising a gas supply unit configured to supply a processing gas into a processing container, wherein the processing gas includes an organic acid ammonium salt, an organic acid amine salt, an organic acid amide, and an organic acid hydrazide.
  • the processing gas includes an organic acid ammonium salt, an organic acid amine salt, an organic acid amide, and an organic acid hydrazide.
  • the above-described problem is solved by holding a substrate to be processed and heating the substrate to be processed, a processing container having the holding table therein,
  • a recording medium storing a program for operating a substrate processing method by a substrate processing apparatus provided with a gas supply unit for supplying a processing gas in a processing container by a computer, wherein the substrate processing method includes: On the treated substrate, organic acid ammonium salt, organic acid amine
  • a recording medium comprising a processing step of supplying the processing gas containing a substance containing at least one of a salt, an organic acid amide, and an organic acid hydrazide and heating the substrate to be processed To solve.
  • the present invention it is possible to reduce the influence of metal contamination when an oxide film formed on a metal layer is removed in a semiconductor device manufacturing process.
  • FIG. 1 shows a substrate processing apparatus according to Embodiment 1.
  • FIG. 2 is a view showing a substrate processing apparatus according to a second embodiment.
  • FIG. 3A is a view (No. 1) showing a method for manufacturing a semiconductor device (substrate treatment method) according to Embodiment 3.
  • FIG. 3B is a diagram (part 2) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
  • FIG. 3C is a diagram (part 3) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
  • FIG. 3D is a diagram (part 4) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
  • FIG. 3E is a diagram (part 5) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
  • a substrate processing method is a substrate processing method for a substrate to be processed, in which an insulating film and a metal layer are formed, wherein an organic acid ammonium salt, an organic acid amine salt, an organic acid salt is formed on the substrate to be processed It has a processing step of supplying a vapor (hereinafter sometimes referred to as a processing gas in the sentence) of a substance containing at least one of acid amide and organic acid hydrazide and heating the substrate to be processed. As les.
  • At least one of the organic acid ammonium salt, the organic acid amine salt, the organic acid amide, and the organic acid hydrazide has a low corrosiveness to the metal material. It is characterized by the use of vapor of a substance containing one. For this reason, the influence of corroding piping made of a metal material for supplying a processing gas, a processing container of a substrate processing apparatus, etc. is suppressed, and substrate processing with reduced metal contamination is possible.
  • the above-described processing gas has a feature that a metal (for example, Cu) oxide film can be stably removed as compared with formic acid and acetic acid conventionally used.
  • a metal for example, Cu
  • formic acid or acetic acid vapor both monomers and dimers are formed, and the ratio of these formations varies greatly due to slight differences in conditions, so the metal reduction reaction may become unstable. is there.
  • the dehydration treatment of the insulating film (interlayer insulating film) formed around the metal wiring is performed. There is an effect that makes it possible to perform.
  • the interlayer insulating film made of the above-mentioned low-k material often takes in moisture into the film, which may lead to a decrease in the insulating property of the interlayer insulating film and an increase in the dielectric constant. . Therefore, in the substrate processing method according to the present invention, by using the processing gas, it is possible to perform dehydration processing of the interlayer insulating film as well as metal reduction processing.
  • Cu reduction treatment and interlayer insulation film dehydration treatment using the processing gas can be performed at a low temperature (300 ° C or less), and are susceptible to damage at high temperatures. It is suitable when applied to the formation of a semiconductor device using an interlayer insulating film made of k material.
  • FIG. 1 is a diagram schematically showing an example of the configuration of a substrate processing apparatus according to Embodiment 1 of the present invention.
  • a substrate processing apparatus 100 according to the present embodiment has a processing container 101 in which a processing space 101A is defined.
  • a holding base 103 on which a heater 103A that holds the substrate W to be processed and heats the substrate W to be processed is installed.
  • the heater 103A is connected to a power source 104, and is configured to be able to heat the substrate to be processed W to a desired temperature.
  • the processing space 101A is evacuated from an exhaust line 105 connected to the processing container 101, and is maintained in a reduced pressure state.
  • the exhaust line 105 is connected to an exhaust pump 106 via a pressure adjustment valve 105A, so that the processing space can be brought into a reduced pressure state of a desired pressure.
  • a gas supply unit 102 having a shower head structure is installed on the side of the processing container 101 facing the holding table 103.
  • a gas supply line 107 is connected to the gas supply unit 102. From the gas supply line 107, for example, at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is used. Process gas consisting of vapors of one containing material is supplied.
  • the processing gas supplied to the gas supply unit 102 is supplied to the processing space 101A through a plurality of gas holes 102A formed in the gas supply unit. Supply to the processing space 101A
  • the processed gas reaches the substrate to be processed W heated to a predetermined temperature by the heater 103A, for example, removal of an oxide film of Cu wiring (Cu reduction) formed on the substrate to be processed W, Alternatively, the dehydration treatment of the insulating film (interlayer insulating film) formed on the substrate to be processed W is performed.
  • the gas supply line 107 is provided with a valve 108, a mass flow controller (MFC) 109 force S, and at least one of an organic acid ammonium salt, an organic acid amine salt, an organic acid amide, and an organic acid hydrazide. In any case, it is connected to the raw material supply means 110 that holds the raw material 110a made of the substance including four powers.
  • the raw material supply means 110 is provided with a heater 110A, and the raw material 110a is vaporized (or sublimated) by being heated by the heater 110A. The vaporized raw material 110a (processing gas) is supplied from the gas supply line 107 to the processing space 101A.
  • the raw material 110a is vaporized or sublimated, or when the vaporized or sublimated raw material 110a (processing gas) is supplied to the processing space 101A, for example, Ar or N, or
  • the raw material may be vaporized by a method using a vaporizer by so-called liquid injection.
  • control means 100A The operation of the substrate processing apparatus 100 related to substrate processing is controlled by the control means 100A, and the control means 100A is controlled based on a program stored in the computer 100B. It has become. These wirings are not shown.
  • the control means 100A includes a temperature control means 100a, a gas control means 100b, and a pressure control means 100c.
  • the temperature control means 100 a controls the temperature of the holding table 103 by controlling the power source 104, and controls the temperature of the substrate W to be processed heated by the holding table 103.
  • the gas control means 100b controls the opening and closing of the valve 108 and the flow rate control by the MFC 109, and controls the state of the processing gas supplied to the processing space 101A. Further, the pressure control means 100c controls the opening degree of the exhaust pump 106 and the pressure adjusting valve 105A so that the processing space 101A has a predetermined pressure.
  • the control means 100A is controlled by a computer 100B, and The plate processing apparatus 100 is operated by the computer 100B.
  • the computer 100B includes a CPU 100d, a recording medium 100e, an input unit 100f, a memory 100g, a communication unit 100h, and a display unit 100i.
  • a program for a substrate processing method related to substrate processing is recorded on the recording medium 100e, and the substrate processing is performed based on the program.
  • the program may be input from the communication unit 100h or may be input from the input unit 100f.
  • FIG. 2 is a diagram schematically showing a substrate processing apparatus 100X according to Embodiment 2 of the present invention.
  • the same reference numerals are given to the parts described above, and the description will be omitted. Further, parts not specifically described are the same as those of the substrate processing apparatus of the first embodiment.
  • a substance containing at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is used.
  • water vapor (HO) is supplied.
  • a gas mixing unit 102A connected to the gas supply unit 102 is installed, and further, water vapor (HO) is supplied from the water vapor generator 112 to the gas mixing unit 102A. It is configured as follows.
  • water vapor is supplied from the gas supply line 111 to the reaction promotion chamber 102B installed outside the gas supply unit 102.
  • the gas supply line 111 is connected to the reaction promoting chamber 102B together with the gas supply line 107 so that the processing gas and HO are supplied.
  • the mixed process gas and H 2 O are passed through the gas supply unit 102.
  • a heater 102b is installed outside the reaction promoting chamber 102B, and the mixed gas of the processing gas and H 2 O has a predetermined temperature (the predetermined temperature).
  • the temperature may be higher than the temperature of the substrate to be processed).
  • the gas supply line 111 is connected to a water vapor generator 112.
  • the water steam generator 112 is supplied with O power from the gas line 113 and H from the gas line 117, and is steamed.
  • the gas line 113 is provided with a valve 114 and an MFC 115, and O
  • the gas line 117 includes a valve 118, MFC. 119 is installed and connected to the H supply 120.
  • valves 114 and 118 are opened and closed, the MFCs 115 and 119 are controlled, and the water vapor generator 112 is further controlled to control the H 2 O supplied from the gas supply line 111.
  • an insulating film is formed so as to cover an element (not shown) such as a MOS transistor formed on a semiconductor substrate made of silicon (the substrate W to be processed).
  • a silicon oxide film 201 is formed.
  • a wiring layer (not shown) made of, for example, W (tungsten) electrically connected to the element, and a wiring layer 202 made of, for example, Cu connected to the wiring layer are formed.
  • a first insulating layer (interlayer insulating film) 203 is formed on the silicon oxide film 201 so as to cover the wiring layer 202.
  • a groove portion 204a and a hole portion 204b are formed in the first insulating layer 203.
  • a wiring portion 204 made of Cu and made of trench wiring and via wiring is formed, and this is electrically connected to the wiring layer 202 described above. .
  • a Cu diffusion preventing film 204c is formed between the first insulating layer 203 and the wiring portion 204.
  • the Cu diffusion prevention film 204c has a function of preventing Cu from diffusing from the wiring portion 204 to the first insulating layer 203.
  • an insulating layer 205 (Cu diffusion preventing layer) and a second insulating layer (interlayer insulating film) 206 are formed so as to cover the wiring portion 204 and the first insulating layer 203.
  • the wiring portion 204 can also be formed by a method similar to the method described below.
  • a groove 207a and a hole 207b are formed in the second insulating layer 206 by, for example, a dry etching method or the like.
  • a part of the wiring portion 204 made of Cu is exposed from the opening formed in the second insulating layer 206.
  • An oxide film (not shown) is formed on the exposed surface layer of the wiring part 204.
  • the substrate processing method described above is applied using the substrate processing apparatus 100 or the substrate processing apparatus 100X, and the oxide film of the exposed Cu wiring is removed.
  • Cu reduction treatment a substance (processing gas) containing at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide vaporized or sublimated on the substrate to be processed is supplied.
  • the substrate to be processed is heated to remove the Cu oxide film.
  • the temperature of the substrate to be processed is higher than that in the case where the reduction process is performed using H or NH.
  • the temperature can be lowered, for example, treatment at 300 ° C. or lower is possible.
  • the substrate can be processed at a low temperature of 300 ° C. or lower as in this embodiment. This is particularly preferable.
  • the temperature of the substrate to be processed is too low, the reduction reaction is not sufficiently promoted, so that the temperature is preferably 100 ° C or higher. That is, the temperature of the substrate to be processed is preferably 100 ° C. to 300 ° C.
  • this step it is possible to perform a Cu reduction process and a dehydration process of the interlayer insulating film.
  • the processing gas is supplied to the second insulating layer 206 and heated, so that the dehydration process of the second insulating layer 206 is promoted, and the electric power of the second insulating layer 206 is increased. Effects such as reduction of dielectric constant and improvement of withstand voltage are obtained.
  • the effect of improving the electrical characteristics by such dehydration can be obtained, for example, even when the second insulating layer 206 is a silicon oxide film (SiO film).
  • Layer 206 is a silicon oxide film (SiO film).
  • low dielectric constant material low dielectric constant interlayer insulating film
  • a porous film or a hook There is a film containing element.
  • the substrate processing apparatus 100X is used to supply H 2 O onto the substrate to be processed in this step.
  • the amount of H 2 O supplied should be increased in consideration of the stability of the reduction treatment.
  • the organic acid constituting the organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is, for example, one made of carboxylic acid. be able to.
  • the processing gas used in this example is an organic acid ammonium salt or an organic acid amine salt.
  • Rl_COO_NR2R3R4R5 A functional group in which at least a part of the hydrogen atoms constituting the group or hydrocarbon group are substituted with halogen atoms.
  • the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • Specific halogen atoms can include fluorine, chlorine, bromine and iodine.
  • organic acid ammonium salt and organic acid amine salt examples include organic acid ammonium salt (R 1COONH), organic acid methylamine salt, organic acid ethylamine salt, organic acid tube.
  • Primary amine salts such as tyramine salts, or secondary amine salts such as organic acid dimethylamine salts, organic acid ethylmethylamine salts, organic acid jetylamine salts, organic acid trimethylamine salts, organic acid jetylmethylamine salts, organic There are tertiary amine salts such as ethyldimethylamine salt and organic acid trimethylamine salt, or quaternary ammonium salts such as organic acid tetramethylammonium and organic acid triethylmethylammonium.
  • the organic acid amide that is a processing gas used in this example is R6 -CO-NH2 (R6 is a hydrogen atom, a hydrocarbon group, or a hydrogen atom constituting a hydrocarbon group. A functional group in which a part is substituted with a halogen atom.)
  • Specific hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like.
  • Specific halogen atoms include fluorine, chlorine, bromine and iodine.
  • Ability to do S for example, as an example of organic acid amide, carboxylic acid amide (RCONH) is
  • the organic acid hydrazide which is a processing gas used in this example, is R7-CO-NH0NH2 (R7 is at least one of hydrogen atoms constituting a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. A functional group in which a part is substituted with a halogen atom.)
  • Specific hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like.
  • Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.
  • Examples of the organic acid include carboxylic acids such as acetic acid, formic acid, propionic acid, butyric acid, acetic acid formic acid, and valeric acid.
  • carboxylic acids such as acetic acid, formic acid, propionic acid, butyric acid, acetic acid formic acid, and valeric acid.
  • the flow rate of the processing gas is 1 to 1000 sccm
  • the pressure of the processing space 101A is 1 to lOOOPa
  • the temperature of the substrate to be processed is 100 to 300 ° C.
  • the processing time is The above processing can be performed for 1 to 180 seconds.
  • the flow rate of water vapor is preferably 1 to lOOOOsccm.
  • the temperature of the reaction promoting chamber 102B is preferably higher than the temperature of the substrate to be processed.
  • a Cu diffusion preventing film 207c is formed on the second insulating layer 206 including the inner wall surfaces of the groove portion 207a and the hole portion 207b and on the exposed surface of the wiring portion 204.
  • the film is formed.
  • the Cu diffusion preventing film 207c is, for example, a refractory metal film, a nitride film thereof, or a laminated film force of the refractory metal film and the nitride film.
  • the Cu diffusion prevention film 207c is made of a Ta / TaN film, a WN film, or a TiN film, and can be formed by a method such as sputtering or CVD.
  • Such a Cu diffusion barrier film can also be formed by the so-called ALD method.
  • a wiring portion 207 made of Cu is formed on the Cu diffusion preventing film 207c including the groove portion 207a and the hole portion 207b.
  • the wiring portion 207 can be formed by electric field measurement of Cu. Further, the wiring portion 207 may be formed by a CVD method or an ALD method.
  • the substrate surface is planarized by a chemical mechanical polishing (CMP) method.
  • CMP chemical mechanical polishing
  • a 2 + n insulating layer (n is a natural number) is further formed on the second insulating layer, and a wiring made of Cu is formed on each insulating layer by the above method. It is possible to form a semiconductor device having a multilayer wiring structure.
  • the Cu wiring is mainly described as an example of the metal wiring formed in the insulating layer.
  • the present invention is not limited to this.
  • this embodiment can also be applied to metals (wirings) such as Ag, W, Co, Ru, Ti, Ta, etc. in addition to Cu.
  • FIG. 4 shows a substrate processing apparatus 100Y that is a modification of the substrate processing apparatus 100 described in the first embodiment.
  • the same reference numerals are given to the parts described above, and the description is omitted.
  • a raw material supply means 310 is installed in place of the raw material supply means 110 installed in the substrate processing apparatus 100.
  • the raw material supply means 310 is configured to vaporize or sublimate the raw material 110a by a so-called publishing method and supply it to the processing space 101A from the gas supply line 107.
  • the raw material supply means 310 is supplied with an inert gas (for example, He) as a carrier gas from a gas line 311, and the vaporized or sublimated raw material is supplied to the processing vessel together with the carrier gas.
  • an inert gas for example, He
  • the removal of the oxide film formed on Cu can be stably and efficiently performed while reducing the influence of metal contamination.
  • the interlayer insulating film can be dehydrated.
  • the above-described method makes it possible to perform Cu oxide film removal and dehydration treatment of the interlayer insulating layer, which were conventionally performed in separate steps, at substantially the same time, thereby simplifying the semiconductor device manufacturing process. It has become.
  • the removal of the oxide film of the metal layer and the dehydration treatment of the interlayer insulating layer are performed simultaneously.
  • the force explaining the example performed in the present invention is not limited to this.
  • the organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide described in the above-mentioned examples can be used as the processing gas.
  • the substrate processing method and the substrate processing apparatus can be similarly performed using the same method and apparatus as those described in the above embodiments.
  • the substrate processing method of the present invention is applied to the step of removing the Cu surface oxide film of the lower layer wiring exposed in the opening formed by etching the insulating layer.
  • the present invention may be applied to the case where the Cu surface oxide film is removed in another process.
  • the present invention may be applied to a seed layer or a wiring layer after it is formed or after CMP.
  • the present invention it is possible to reduce the influence of metal contamination when an oxide film formed on a metal wiring is removed in a semiconductor device manufacturing process.

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Abstract

Substrate treating apparatus (100) including support table (103) for not only supporting of treatment object substrate (W) but also heating of the treatment object substrate (W); treatment vessel (101) having the support table (103) disposed therein; and gas supply section (102) for supplying of treating gas into the treatment vessel (101), characterized in that the treating gas contains at least one member selected from among an organic salt, an organic acid amine salt, an organic acid amide and an organic acid hydrazide.

Description

明 細 書  Specification
基板処理方法、半導体装置の製造方法、基板処理装置、および記録媒 体  Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and recording medium
技術分野  Technical field
[0001] 本発明は、金属配線を用いた半導体装置の製造方法に関する。  The present invention relates to a method for manufacturing a semiconductor device using metal wiring.
背景技術  Background art
[0002] 半導体装置の高性能化に伴い、半導体装置の配線材料として抵抗値の小さい Cu を用いることが広く普及してきている。しかし、 Cuは酸化されやすい性質を有している ため、例えばダマシン法によって Cuの多層配線構造を形成する工程において、層間 絶縁膜から露出した Cu配線が酸化してしまう場合がある。このため、酸化された Cu を還元により除去（クリーニング）するため、 NHや Hなどの還元性を有するガスが用  [0002] With the high performance of semiconductor devices, the use of Cu having a low resistance value as a wiring material for semiconductor devices has become widespread. However, since Cu is easily oxidized, Cu wiring exposed from the interlayer insulating film may be oxidized in the process of forming a Cu multilayer wiring structure by, for example, the damascene method. For this reason, reducing gases such as NH and H are used to remove (clean) oxidized Cu by reduction.
3 2  3 2
いられる場合があった。  There was a case.
[0003] しかし、 NHや Hを用いた場合には、 Cuの還元処理の処理温度を高く（例えば 30  [0003] However, when NH or H is used, the treatment temperature of Cu reduction is increased (for example, 30
3 2  3 2
0°C以上）する必要があつたため、 Cu配線の周囲に形成されている、いわゆる Low _k材料よりなる層間絶縁膜にダメージが生じる懸念があった。そのため、例えば蟻 酸や酢酸などを気化して処理ガスとして用いることで、 Cuの還元を低温で行うことが 提案されていた。  Therefore, there was a concern that the interlayer insulating film made of the so-called Low_k material formed around the Cu wiring might be damaged. For this reason, it has been proposed to reduce Cu at a low temperature by evaporating, for example, formic acid or acetic acid and using it as a processing gas.
[0004] しかし、上記の蟻酸や酢酸は、基板処理装置に用いられている金属材料に対する 腐食性が強ぐそのために基板処理を行う場合に被処理基板が金属で汚染されてし まう懸念が生じていた。  [0004] However, the formic acid and acetic acid described above are highly corrosive to the metal materials used in the substrate processing apparatus. Therefore, there is a concern that the substrate to be processed may be contaminated with the metal when the substrate is processed. It was.
[0005] 例えば、基板処理装置に用いられる、処理ガスや原料を輸送する配管は、ステンレ ス合金などの金属材料により形成されていることが大半である。しかし、蟻酸や酢酸 は、このような金属材料に対する腐食性があり、このために、基板処理装置が金属で 汚染され、そのために被処理基板が金属で汚染されてしまう懸念があった。  [0005] For example, piping for transporting processing gas and raw materials used in a substrate processing apparatus is mostly formed of a metal material such as a stainless alloy. However, formic acid and acetic acid are corrosive to such metal materials. For this reason, there has been a concern that the substrate processing apparatus is contaminated with metal, and therefore the substrate to be processed is contaminated with metal.
特許文献 1：特許第 3373499号公報  Patent Document 1: Japanese Patent No. 3373499
発明の開示  Disclosure of the invention
発明が解決しょうとする課題 [0006] そこで、本発明では、上記の問題を解決した、新規で有用な基板処理方法、半導 体装置の製造方法、基板処理装置、および当該基板処理方法を記憶した記録媒体 を提供することを目的としてレ、る。 Problems to be solved by the invention Accordingly, the present invention provides a novel and useful substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a recording medium storing the substrate processing method, which solve the above-described problems. For the purpose.
[0007] 本発明の具体的な課題は、半導体装置の製造工程において、金属配線に形成さ れる酸化膜を除去する場合の金属汚染の影響を低減することである。  A specific problem of the present invention is to reduce the influence of metal contamination when an oxide film formed on a metal wiring is removed in a semiconductor device manufacturing process.
課題を解決するための手段  Means for solving the problem
[0008] 本発明の第 1の観点では、上記の課題を、絶縁膜と金属層が形成された、被処理 基板の基板処理方法であって、前記被処理基板上に、有機酸アンモニゥム塩、有機 酸ァミン塩、有機酸アミド、および有機酸ヒドラジドのうち、少なくともいずれ力 1つを含 む物質の蒸気を供給するとともに前記被処理基板を加熱する処理工程を有すること を特徴とする基板処理方法により、解決する。  [0008] In a first aspect of the present invention, there is provided a substrate processing method for a substrate to be processed in which an insulating film and a metal layer are formed, wherein an organic acid ammonium salt is formed on the substrate to be processed, A substrate processing method comprising: supplying a vapor of a substance containing at least one of an organic acid amine salt, an organic acid amide, and an organic acid hydrazide and heating the substrate to be processed. To solve.
[0009] また、本発明の第 2の観点では、上記の課題を、金属配線と層間絶縁膜を含む、半 導体装置の製造方法であって、前記金属配線と前記層間絶縁膜が形成された被処 理基板上に、有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒ ドラジドのうち、少なくともいずれ力 1つを含む物質の蒸気を供給すると共に前記被処 理基板を加熱する処理工程を含むことを特徴とする半導体装置の製造方法により、 解決する。  [0009] Further, according to a second aspect of the present invention, there is provided a semiconductor device manufacturing method including a metal wiring and an interlayer insulating film, wherein the metal wiring and the interlayer insulating film are formed. A vapor of a substance containing at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is supplied onto the substrate to be processed and the substrate to be processed is heated. This is solved by a method for manufacturing a semiconductor device, which includes a processing step.
[0010] また、本発明の第 3の観点では、上記の課題を、被処理基板を保持すると共に該被 処理基板を加熱する保持台と、前記保持台を内部に備えた処理容器と、前記処理 容器内に、処理ガスを供給するガス供給部と、を備えた基板処理装置であって、前 記処理ガスは、有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機 酸ヒドラジドのうち、少なくともいずれ力 4つを含むことを特徴とする基板処理装置によ り、解決する。  [0010] Further, in a third aspect of the present invention, the above-described problem is solved by holding a substrate to be processed and heating the substrate to be processed, a processing container having the holding table therein, A substrate processing apparatus comprising a gas supply unit configured to supply a processing gas into a processing container, wherein the processing gas includes an organic acid ammonium salt, an organic acid amine salt, an organic acid amide, and an organic acid hydrazide. The problem is solved by a substrate processing apparatus characterized by including at least four of them.
[0011] また、本発明の第 4の観点では、上記の課題を、被処理基板を保持すると共に該被 処理基板を加熱する保持台と、前記保持台を内部に備えた処理容器と、前記処理 容器内に、処理ガスを供給するガス供給部と、を備えた基板処理装置による基板処 理方法を、コンピュータによって動作させるプログラムを記憶した記録媒体であって、 前記基板処理方法は、前記被処理基板上に、有機酸アンモニゥム塩、有機酸ァミン 塩、有機酸アミド、および有機酸ヒドラジドのうち、少なくともいずれ力 1つを含む物質 を含む前記処理ガスを供給するとともに前記被処理基板を加熱する処理工程を有す ることを特徴とする記録媒体により、解決する。 [0011] Further, in a fourth aspect of the present invention, the above-described problem is solved by holding a substrate to be processed and heating the substrate to be processed, a processing container having the holding table therein, A recording medium storing a program for operating a substrate processing method by a substrate processing apparatus provided with a gas supply unit for supplying a processing gas in a processing container by a computer, wherein the substrate processing method includes: On the treated substrate, organic acid ammonium salt, organic acid amine A recording medium comprising a processing step of supplying the processing gas containing a substance containing at least one of a salt, an organic acid amide, and an organic acid hydrazide and heating the substrate to be processed To solve.
発明の効果  The invention's effect
[0012] 本発明によれば、半導体装置の製造工程において、金属層に形成される酸化膜を 除去する場合の金属汚染の影響を低減することが可能となる。  According to the present invention, it is possible to reduce the influence of metal contamination when an oxide film formed on a metal layer is removed in a semiconductor device manufacturing process.
図面の簡単な説明  Brief Description of Drawings
[0013] [図 1]実施例 1による基板処理装置を示す図である。  FIG. 1 shows a substrate processing apparatus according to Embodiment 1.
[図 2]実施例 2のよる基板処理装置を示す図である。  FIG. 2 is a view showing a substrate processing apparatus according to a second embodiment.
[図 3A]実施例 3による半導体装置の製造方法 (基板処理方法）を示す図（その 1)で ある。  FIG. 3A is a view (No. 1) showing a method for manufacturing a semiconductor device (substrate treatment method) according to Embodiment 3.
[図 3B]実施例 3による半導体装置の製造方法 (基板処理方法）を示す図（その 2)で ある。  FIG. 3B is a diagram (part 2) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
[図 3C]実施例 3による半導体装置の製造方法 (基板処理方法）を示す図（その 3)で ある。  FIG. 3C is a diagram (part 3) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
[図 3D]実施例 3による半導体装置の製造方法 (基板処理方法)を示す図（その 4)で ある。  FIG. 3D is a diagram (part 4) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
[図 3E]実施例 3による半導体装置の製造方法 (基板処理方法)を示す図（その 5)で ある。  FIG. 3E is a diagram (part 5) illustrating the semiconductor device manufacturing method (substrate processing method) according to Example 3.
[図 4]図 1の基板処理装置の変形例である。  4 is a modification of the substrate processing apparatus of FIG.
符号の説明  Explanation of symbols
[0014] 100, 100A 基板処理装置 [0014] 100, 100A substrate processing apparatus
100A 制御手段  100A control means
100a 温度制御手段  100a Temperature control means
100b ガス制御手段  100b Gas control means
100c 圧力制御手段  100c Pressure control means
100B コンピュータ  100B computer
100d CPU 100e 記録媒体 100d CPU 100e recording medium
lOOf 入力手段  lOOf input means
100g メモリ  100g memory
100h 通信手段  100h Communication means
100Ϊ 表示手段  100Ϊ Display means
101 処理容器  101 Processing container
101 A 処理空間  101 A processing space
102 ガス供給部  102 Gas supply unit
102A ガス穴  102A Gas hole
102B 反応促進室  102B reaction chamber
102b ヒータ  102b heater
103 保持台  103 Holding stand
103A ヒータ  103A heater
104 電源  104 Power supply
105 排気ライン  105 Exhaust line
105A 圧力調整バルブ  105A pressure regulating valve
106 排気ポンプ  106 Exhaust pump
107, 111 ガス供給ライン  107, 111 Gas supply line
110 原料供給手段 110  110 Raw material supply means 110
110a 原料  110a Raw material
110A ヒータ  110A heater
112 水蒸気発生器  112 Steam generator
113, 117 ガスライン  113, 117 gas lines
108, 114, 118 ノ ノレブ  108, 114, 118
109, 115, 119 MFC  109, 115, 119 MFC
116, 120 ガス供給源  116, 120 Gas supply source
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
次に、本発明の実施の形態に関して説明する。 [0016] 本発明による基板処理方法は、絶縁膜と金属層が形成された、被処理基板の基板 処理方法であって、前記被処理基板上に、有機酸アンモニゥム塩、有機酸ァミン塩、 有機酸アミド、および有機酸ヒドラジドのうち、少なくともいずれ力 1つを含む物質の蒸 気（以降文中処理ガスと呼ぶ場合がある）を供給するとともに前記被処理基板を加熱 する処理工程を有することを特徴としてレ、る。 Next, an embodiment of the present invention will be described. A substrate processing method according to the present invention is a substrate processing method for a substrate to be processed, in which an insulating film and a metal layer are formed, wherein an organic acid ammonium salt, an organic acid amine salt, an organic acid salt is formed on the substrate to be processed It has a processing step of supplying a vapor (hereinafter sometimes referred to as a processing gas in the sentence) of a substance containing at least one of acid amide and organic acid hydrazide and heating the substrate to be processed. As les.
[0017] 従来、基板処理に用いられている蟻酸や酢酸は、例えばこれらのガス (液体）を供 給する配管を構成するステンレス合金などの金属材料に対する腐食性があるため、 基板処理装置内が金属で汚染され、そのために被処理基板が金属で汚染されてし まう懸念があった。  [0017] Conventionally, formic acid and acetic acid used for substrate processing are corrosive to metal materials such as stainless alloys that constitute piping for supplying these gases (liquids). There was concern that the substrate to be treated would be contaminated with metal, which could contaminate the substrate to be processed.
[0018] そこで、本発明による基板処理方法では、金属材料に対する腐食性が少なレ、、有 機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジドのうち、 少なくともいずれ力、 1つを含む物質の蒸気を用いていることが特徴である。このため、 処理ガスを供給する金属材料よりなる配管や、基板処理装置の処理容器などを腐食 させる影響が抑制され、金属汚染を抑制した基板処理が可能となっている。  [0018] Therefore, in the substrate processing method according to the present invention, at least one of the organic acid ammonium salt, the organic acid amine salt, the organic acid amide, and the organic acid hydrazide has a low corrosiveness to the metal material. It is characterized by the use of vapor of a substance containing one. For this reason, the influence of corroding piping made of a metal material for supplying a processing gas, a processing container of a substrate processing apparatus, etc. is suppressed, and substrate processing with reduced metal contamination is possible.
[0019] また、上記の処理ガスは、従来用いられていた蟻酸や酢酸に比べて、安定に金属（ 例えば Cu)の酸化膜の除去を行うことが可能な特徴を有している。例えば、蟻酸や酢 酸の蒸気では、モノマーとダイマーの双方が形成され、また僅かな条件の違いにより これらの形成される割合が大きく変動するため、金属の還元反応が不安定になる場 合がある。  [0019] Further, the above-described processing gas has a feature that a metal (for example, Cu) oxide film can be stably removed as compared with formic acid and acetic acid conventionally used. For example, with formic acid or acetic acid vapor, both monomers and dimers are formed, and the ratio of these formations varies greatly due to slight differences in conditions, so the metal reduction reaction may become unstable. is there.
[0020] 本発明では、上記の蟻酸や酢酸に換えて、安定に金属の還元を行うことが可能な 処理ガスを用いており、そのために、金属の還元を安定に、効率よく実施することが 可能となっている。  [0020] In the present invention, instead of the formic acid or acetic acid described above, a processing gas capable of stably reducing a metal is used, and for this reason, the metal can be reduced stably and efficiently. It is possible.
[0021] また、金属の還元に上記の処理ガスを用いることで、金属の還元処理に加えて、金 属配線 (例えば Cu配線）の周囲に形成された絶縁膜 (層間絶縁膜）の脱水処理を行 うことが可能になる効果を奏する。  [0021] Further, by using the above processing gas for metal reduction, in addition to the metal reduction treatment, the dehydration treatment of the insulating film (interlayer insulating film) formed around the metal wiring (for example, Cu wiring) is performed. There is an effect that makes it possible to perform.
[0022] 例えば、金属配線を用いた半導体装置では、配線遅延を低減するために、 Cuを用 いて配線抵抗を小さくすると共に、層間絶縁膜に誘電率の低い、いわゆる Low_k 材料を用いることが好ましい。 [0023] 上記の Low— k材料よりなる層間絶縁膜は、膜中に水分を取り込んでしまうことが多 ぐこのために層間絶縁膜の絶縁性の低下や誘電率の増大を招く場合があった。そ こで、本発明による基板処理方法では、前記処理ガスを用いることで、金属の還元処 理と共に層間絶縁膜の脱水処理を行うことが可能になっている。 For example, in a semiconductor device using metal wiring, in order to reduce wiring delay, it is preferable to use Cu to reduce wiring resistance and to use a so-called Low_k material having a low dielectric constant for the interlayer insulating film. . [0023] The interlayer insulating film made of the above-mentioned low-k material often takes in moisture into the film, which may lead to a decrease in the insulating property of the interlayer insulating film and an increase in the dielectric constant. . Therefore, in the substrate processing method according to the present invention, by using the processing gas, it is possible to perform dehydration processing of the interlayer insulating film as well as metal reduction processing.
[0024] また、前記処理ガスを用いた Cuの還元処理および層間絶縁膜の脱水処理は、低 温（300°C以下）での処理が可能であり、高温でダメージを受けやすレ、 Low— k材料 よりなる層間絶縁膜を用いた半導体装置の形成に適用すると好適である。  [0024] In addition, Cu reduction treatment and interlayer insulation film dehydration treatment using the processing gas can be performed at a low temperature (300 ° C or less), and are susceptible to damage at high temperatures. It is suitable when applied to the formation of a semiconductor device using an interlayer insulating film made of k material.
[0025] 次に、上記の基板処理方法、該基板処理方法を適用した半導体装置の製造方法 、該基板処理方法を実施する基板処理装置、および該基板処理方法を記憶した記 録媒体の具体的な例について、図面に基づき以下に説明する。  [0025] Next, specific examples of the substrate processing method, a method for manufacturing a semiconductor device to which the substrate processing method is applied, a substrate processing apparatus for performing the substrate processing method, and a recording medium storing the substrate processing method Specific examples will be described below with reference to the drawings.
実施例 1  Example 1
[0026] 図 1は、本発明の実施例 1による基板処理装置の構成の例を模式的に示した図で ある。図 1を参照するに、本実施例による基板処理装置 100は、内部に処理空間 10 1Aが画成される処理容器 101を有している。前記処理空間 101Aには、被処理基板 Wを保持し、該被処理基板 Wを加熱するヒータ 103Aが設置された保持台 103が設 置されている。前記ヒータ 103Aは、電源 104に接続されており、前記被処理基板 W を所望の温度に加熱することが可能に構成されている。  FIG. 1 is a diagram schematically showing an example of the configuration of a substrate processing apparatus according to Embodiment 1 of the present invention. Referring to FIG. 1, a substrate processing apparatus 100 according to the present embodiment has a processing container 101 in which a processing space 101A is defined. In the processing space 101A, a holding base 103 on which a heater 103A that holds the substrate W to be processed and heats the substrate W to be processed is installed. The heater 103A is connected to a power source 104, and is configured to be able to heat the substrate to be processed W to a desired temperature.
[0027] また、前記処理空間 101Aは、前記処理容器 101に接続された排気ライン 105から 真空排気され、減圧状態に保持される。前記排気ライン 105は、圧力調整バルブ 10 5Aを介して排気ポンプ 106に接続され、前記処理空間を所望の圧力の減圧状態と することが可能になっている。  In addition, the processing space 101A is evacuated from an exhaust line 105 connected to the processing container 101, and is maintained in a reduced pressure state. The exhaust line 105 is connected to an exhaust pump 106 via a pressure adjustment valve 105A, so that the processing space can be brought into a reduced pressure state of a desired pressure.
[0028] また、処理容器 101の、前記保持台 103に対向する側には、例えばシャワーヘッド 構造よりなるガス供給部 102が設置されてレ、る。前記ガス供給部 102にはガス供給ラ イン 107が接続され、該ガス供給ライン 107より、例えば、有機酸アンモニゥム塩、有 機酸ァミン塩、有機酸アミド、および有機酸ヒドラジドのうち、少なくともいずれ力 1つを 含む物質の蒸気よりなる処理ガスが供給される。  [0028] In addition, a gas supply unit 102 having a shower head structure, for example, is installed on the side of the processing container 101 facing the holding table 103. A gas supply line 107 is connected to the gas supply unit 102. From the gas supply line 107, for example, at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is used. Process gas consisting of vapors of one containing material is supplied.
[0029] 前記ガス供給部 102に供給された処理ガスは、前記ガス供給部に形成された複数 のガス穴 102Aより、前記処理空間 101Aに供給される。前記処理空間 101Aに供給 された処理ガスは、前記ヒータ 103Aによって所定の温度に加熱された前記被処理 基板 Wに到達し、例えば該被処理基板 Wに形成された Cu配線の酸化膜の除去（C uの還元）、または該被処理基板 Wに形成された絶縁膜 (層間絶縁膜）の脱水処理が 行われる。 The processing gas supplied to the gas supply unit 102 is supplied to the processing space 101A through a plurality of gas holes 102A formed in the gas supply unit. Supply to the processing space 101A The processed gas reaches the substrate to be processed W heated to a predetermined temperature by the heater 103A, for example, removal of an oxide film of Cu wiring (Cu reduction) formed on the substrate to be processed W, Alternatively, the dehydration treatment of the insulating film (interlayer insulating film) formed on the substrate to be processed W is performed.
[0030] 前記ガス供給ライン 107には、バルブ 108、質量流量コントローラ（MFC) 109力 S設 置され、さらに有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸 ヒドラジドのうち、少なくともいずれ力 4つを含む物質よりなる原料 110aを保持する原 料供給手段 110に接続されている。前記原料供給手段 110には、ヒータ 110Aが設 置され、前記原料 110aは、該ヒータ 110Aによって加熱されることで気化（または昇 華）する。気化した前記原料 110a (処理ガス）は、前記ガス供給ライン 107から前記 処理空間 101Aに供給される構造になっている。  [0030] The gas supply line 107 is provided with a valve 108, a mass flow controller (MFC) 109 force S, and at least one of an organic acid ammonium salt, an organic acid amine salt, an organic acid amide, and an organic acid hydrazide. In any case, it is connected to the raw material supply means 110 that holds the raw material 110a made of the substance including four powers. The raw material supply means 110 is provided with a heater 110A, and the raw material 110a is vaporized (or sublimated) by being heated by the heater 110A. The vaporized raw material 110a (processing gas) is supplied from the gas supply line 107 to the processing space 101A.
[0031] また、前記原料 110aを気化または昇華させる場合や、気化または昇華した前記原 料 110a (処理ガス）を前記処理空間 101Aに供給する場合に、例えば Arや N、また  [0031] Further, when the raw material 110a is vaporized or sublimated, or when the vaporized or sublimated raw material 110a (processing gas) is supplied to the processing space 101A, for example, Ar or N, or
2 は Heなどのキャリアガスを用いて、当該キャリアガスとともに処理ガスが前記処理空 間 101Aに供給されるようにしてもよい。また、いわゆるリキッドインジェクションによる 気化器を用いた方法により、原料を気化してもよい。  2 may use a carrier gas such as He so that the processing gas is supplied to the processing space 101A together with the carrier gas. Further, the raw material may be vaporized by a method using a vaporizer by so-called liquid injection.
[0032] また、前記基板処理装置 100の、基板処理に係る動作は、制御手段 100Aによつ て制御され、さらに該制御手段 100Aは、コンピュータ 100Bに記憶されたプログラム に基づき、制御される構造になっている。なお、これらの配線は図示を省略している。  [0032] The operation of the substrate processing apparatus 100 related to substrate processing is controlled by the control means 100A, and the control means 100A is controlled based on a program stored in the computer 100B. It has become. These wirings are not shown.
[0033] 前記制御手段 100Aは、温度制御手段 100aと、ガス制御手段 100b、および圧力 制御手段 100cと、を有している。前記温度制御手段 100aは、前記電源 104を制御 することで前記保持台 103の温度を制御し、該保持台 103によって加熱される前記 被処理基板 Wの温度を制御する。  [0033] The control means 100A includes a temperature control means 100a, a gas control means 100b, and a pressure control means 100c. The temperature control means 100 a controls the temperature of the holding table 103 by controlling the power source 104, and controls the temperature of the substrate W to be processed heated by the holding table 103.
[0034] 前記ガス制御手段 100bは、前記バルブ 108の開閉や、前記 MFC109による流量 制御を統括し、前記処理空間 101Aに供給される処理ガスの状態を制御する。さらに 、前記圧力制御手段 100cは、前記排気ポンプ 106および前記圧力調整バルブ 105 Aの開度を制御し、前記処理空間 101Aが所定の圧力となるように制御する。  [0034] The gas control means 100b controls the opening and closing of the valve 108 and the flow rate control by the MFC 109, and controls the state of the processing gas supplied to the processing space 101A. Further, the pressure control means 100c controls the opening degree of the exhaust pump 106 and the pressure adjusting valve 105A so that the processing space 101A has a predetermined pressure.
[0035] また、前記制御手段 100Aは、コンピュータ 100Bによって制御されており、前記基 板処理装置 100は、該コンピュータ 100Bによって動作される。前記コンピュータ 100 Bは、 CPU100d、記録媒体 100e、入力手段 100f、メモリ 100g、通信手段 100h、 および表示手段 100iを有している。例えば、基板処理に係る基板処理方法のプログ ラムは、記録媒体 100eに記録されており、基板処理は当該プログラムに基づき、行 われる。また、当該プログラムは、前記通信手段 100hより入力されたり、または前記 入力手段 100fによって入力されてもよい。 [0035] The control means 100A is controlled by a computer 100B, and The plate processing apparatus 100 is operated by the computer 100B. The computer 100B includes a CPU 100d, a recording medium 100e, an input unit 100f, a memory 100g, a communication unit 100h, and a display unit 100i. For example, a program for a substrate processing method related to substrate processing is recorded on the recording medium 100e, and the substrate processing is performed based on the program. The program may be input from the communication unit 100h or may be input from the input unit 100f.
実施例 2  Example 2
[0036] また、上記の実施例 1による基板処理装置は、以下に示すような構成に変更しても よい。図 2は、本発明の実施例 2による基板処理装置 100Xを模式的に示した図であ る。ただし図中、先に説明した部分には同一の参照符号を付し、説明を省略する。ま た、特に説明しない部分は実施例 1の基板処理装置と同様とする。  [0036] The substrate processing apparatus according to the first embodiment may be changed to the following configuration. FIG. 2 is a diagram schematically showing a substrate processing apparatus 100X according to Embodiment 2 of the present invention. However, in the figure, the same reference numerals are given to the parts described above, and the description will be omitted. Further, parts not specifically described are the same as those of the substrate processing apparatus of the first embodiment.
[0037] 図 2を参照するに、本実施例による基板処理装置 100Xでは、有機酸アンモニゥム 塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジドのうち、少なくともいずれ 力 1つを含む物質の蒸気に加えて、水蒸気 (H O)が供給される構造になっている。  [0037] Referring to FIG. 2, in the substrate processing apparatus 100X according to the present embodiment, a substance containing at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is used. In addition to steam, water vapor (HO) is supplied.
2  2
本実施例による基板処理装置 100Xでは、前記ガス供給部 102に接続される、ガス 混合部 102Aが設置され、さらに当該ガス混合部 102Aには、水蒸気発生器 112より 水蒸気 (H O)が供給されるように構成されている。  In the substrate processing apparatus 100X according to the present embodiment, a gas mixing unit 102A connected to the gas supply unit 102 is installed, and further, water vapor (HO) is supplied from the water vapor generator 112 to the gas mixing unit 102A. It is configured as follows.
2  2
[0038] この場合水蒸気は、ガス供給ライン 111から、前記ガス供給部 102の外側に設置さ れた反応促進室 102Bに供給される。前記反応促進室 102Bには、前記ガス供給ラ イン 107とともに、前記ガス供給ライン 111が接続されて、前記処理ガスと H〇が供  In this case, water vapor is supplied from the gas supply line 111 to the reaction promotion chamber 102B installed outside the gas supply unit 102. The gas supply line 111 is connected to the reaction promoting chamber 102B together with the gas supply line 107 so that the processing gas and HO are supplied.
2 給され、混合される。混合された前記処理ガスと H Oは、前記ガス供給部 102を介し  2 fed and mixed. The mixed process gas and H 2 O are passed through the gas supply unit 102.
2  2
て、前記処理空間 101Aに供給される。また、前記反応促進室 102Bの外側には、ヒ ータ 102bが設置され、前記処理ガスと H Oの混合ガスが所定の温度（当該所定の  And supplied to the processing space 101A. In addition, a heater 102b is installed outside the reaction promoting chamber 102B, and the mixed gas of the processing gas and H 2 O has a predetermined temperature (the predetermined temperature).
2  2
温度は被処理基板の温度より高くてもよい）に加熱される構造になっている。  The temperature may be higher than the temperature of the substrate to be processed).
[0039] また、前記ガス供給ライン 111は、水蒸気発生器 112に接続されている。前記水蒸 気発生器 112には、ガスライン 113より O力 ガスライン 117より Hが供給され、水蒸 Further, the gas supply line 111 is connected to a water vapor generator 112. The water steam generator 112 is supplied with O power from the gas line 113 and H from the gas line 117, and is steamed.
2 2  twenty two
気が生成される。前記ガスライン 113には、バルブ 114、 MFC115が設置され、 O  Qi is generated. The gas line 113 is provided with a valve 114 and an MFC 115, and O
2 供給源 116に接続されている。同様に、前記ガスライン 117には、バルブ 118、 MFC 119が設置され、 H供給源 120に接続されている。前記ガス制御手段 100bは、前 2 Connected to source 116. Similarly, the gas line 117 includes a valve 118, MFC. 119 is installed and connected to the H supply 120. The gas control means 100b
2  2
記バルブ 114, 118の開閉や、前記 MFC115, 119の制御、さらに前記水蒸気発生 器 112の制御を行って、前記ガス供給ライン 111から供給される H Oの制御を行って  The valves 114 and 118 are opened and closed, the MFCs 115 and 119 are controlled, and the water vapor generator 112 is further controlled to control the H 2 O supplied from the gas supply line 111.
2  2
いる。  Yes.
[0040] 上記の基板処理装置を用いて基板処理を行うことで、前記処理空間 101Aに、前 記処理ガスに加えて H〇を供給することが可能となり、 Cuの還元処理がさらに安定  [0040] By performing substrate processing using the above-described substrate processing apparatus, it becomes possible to supply HO to the processing space 101A in addition to the processing gas, and Cu reduction processing is further stabilized.
2  2
し、好ましい。  And preferred.
実施例 3  Example 3
[0041] 次に、上記の基板処理装置 100または基板処理装置 100Xを用いた、半導体装置 の製造方法の一例について、図 3A〜図 3Eに基づき、手順を追って説明する。  [0041] Next, an example of a semiconductor device manufacturing method using the substrate processing apparatus 100 or the substrate processing apparatus 100X will be described step by step based on FIGS. 3A to 3E.
[0042] まず、図 3Aに示した工程における半導体装置では、シリコンからなる半導体基板（ 前記被処理基板 W)上に形成された MOSトランジスタなどの素子（図示せず）を覆う ように絶縁膜、例えばシリコン酸化膜 201が形成されている。当該素子に電気的に接 続されている、例えば W (タングステン)からなる配線層（図示せず）と、これに接続さ れた、例えば Cuからなる配線層 202が形成されている。  First, in the semiconductor device in the process shown in FIG. 3A, an insulating film is formed so as to cover an element (not shown) such as a MOS transistor formed on a semiconductor substrate made of silicon (the substrate W to be processed). For example, a silicon oxide film 201 is formed. A wiring layer (not shown) made of, for example, W (tungsten) electrically connected to the element, and a wiring layer 202 made of, for example, Cu connected to the wiring layer are formed.
[0043] また、前記シリコン酸化膜 201上には、配線層 202を覆うように、第 1の絶縁層（層 間絶縁膜） 203が形成されている。前記第 1の絶縁層 203には、溝部 204aおよびホ ール部 204bが形成されている。前記溝部 204aおよびホール部 204bには、 Cuによ り形成された、トレンチ配線とビア配線からなる配線部 204が形成され、これが前述の 配線層 202と電気的に接続された構成となっている。  A first insulating layer (interlayer insulating film) 203 is formed on the silicon oxide film 201 so as to cover the wiring layer 202. In the first insulating layer 203, a groove portion 204a and a hole portion 204b are formed. In the groove portion 204a and the hole portion 204b, a wiring portion 204 made of Cu and made of trench wiring and via wiring is formed, and this is electrically connected to the wiring layer 202 described above. .
[0044] また、前記第 1の絶縁層 203と前記配線部 204の間には Cu拡散防止膜 204cが形 成されている。前記 Cu拡散防止膜 204cは、前記配線部 204から前記第 1の絶縁層 203へ Cuが拡散するのを防止する機能を有する。さらに、前記配線部 204および前 記第 1の絶縁層 203の上を覆うように絶縁層 205 (Cu拡散防止層）及び第 2の絶縁 層（層間絶縁膜） 206が形成されている。  In addition, a Cu diffusion preventing film 204c is formed between the first insulating layer 203 and the wiring portion 204. The Cu diffusion prevention film 204c has a function of preventing Cu from diffusing from the wiring portion 204 to the first insulating layer 203. Further, an insulating layer 205 (Cu diffusion preventing layer) and a second insulating layer (interlayer insulating film) 206 are formed so as to cover the wiring portion 204 and the first insulating layer 203.
[0045] 以下では、前記第 2の絶縁層 206に、先に説明した基板処理方法を適用して、 Cu の配線を形成して半導体装置を形成する方法を説明する。なお、前記配線部 204に 関しても、以下に説明する方法と同様の方法で形成することが可能である。 [0046] 図 3Bに示す工程では、前記第 2の絶縁層 206に、溝部 207aおよびホール部 207 b (当該ホール部 206は前記絶縁層 205も貫通）を、例えばドライエッチング法などに よって形成する。ここで、前記第 2の絶縁層 206に形成された開口部より、 Cuよりなる 前記配線部 204の一部が露出することになる。露出した前記配線部 204の表層には 、酸化膜 (図示せず)が形成される。 Hereinafter, a method of forming a semiconductor device by forming a Cu wiring by applying the substrate processing method described above to the second insulating layer 206 will be described. Note that the wiring portion 204 can also be formed by a method similar to the method described below. In the step shown in FIG. 3B, a groove 207a and a hole 207b (the hole 206 penetrates the insulating layer 205) are formed in the second insulating layer 206 by, for example, a dry etching method or the like. . Here, a part of the wiring portion 204 made of Cu is exposed from the opening formed in the second insulating layer 206. An oxide film (not shown) is formed on the exposed surface layer of the wiring part 204.
[0047] 次に、図 3Cに示す工程において、前記基板処理装置 100または前記基板処理装 置 100Xを用いて、先に説明した基板処理方法を適用して、露出した Cu配線の酸化 膜の除去（Cuの還元処理)を行う。この場合、被処理基板上に気化または昇華され た、有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジドの うち、少なくともいずれ力、 1つを含む物質 (処理ガス）を供給するとともに、被処理基板 を加熱し、 Cuの酸化膜の除去を行う。  Next, in the step shown in FIG. 3C, the substrate processing method described above is applied using the substrate processing apparatus 100 or the substrate processing apparatus 100X, and the oxide film of the exposed Cu wiring is removed. (Cu reduction treatment). In this case, a substance (processing gas) containing at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide vaporized or sublimated on the substrate to be processed is supplied. At the same time, the substrate to be processed is heated to remove the Cu oxide film.
[0048] この場合、被処理基板の温度は、 Hや NHを用いて還元処理を行う場合に比べて  [0048] In this case, the temperature of the substrate to be processed is higher than that in the case where the reduction process is performed using H or NH.
2 3  twenty three
、低温とすることが可能であり、例えば 300°C以下での処理が可能である。また、例え ば層間絶縁膜が熱によるダメージを受けやすレ、Low— k材料 (低誘電率材料）を含 む場合、本実施例のように 300°C以下による低温で基板処理が可能となることは特 に好ましい。  The temperature can be lowered, for example, treatment at 300 ° C. or lower is possible. In addition, for example, when the interlayer insulating film contains a low-k material (low dielectric constant material) that is easily damaged by heat, the substrate can be processed at a low temperature of 300 ° C. or lower as in this embodiment. This is particularly preferable.
[0049] また、被処理基板の温度は、低すぎると還元反応が十分に促進されないため、 100 °C以上であることが好ましい。すなわち、被処理基板の温度は、 100°C乃至 300°Cで あることが好ましい。  [0049] In addition, if the temperature of the substrate to be processed is too low, the reduction reaction is not sufficiently promoted, so that the temperature is preferably 100 ° C or higher. That is, the temperature of the substrate to be processed is preferably 100 ° C. to 300 ° C.
[0050] また、先に説明したように、本工程において、 Cuの還元処理を行うとともに、層間絶 縁膜の脱水処理を行うことが可能である。この場合、前記第 2の絶縁層 206に前記処 理ガスが供給されて加熱されることで、前記第 2の絶縁層 206の脱水処理が促進さ れて、該第 2の絶縁層 206の電気的な特性が良好となる（例えば、誘電率の低下、耐 電圧の向上など)効果を奏する。  [0050] Further, as described above, in this step, it is possible to perform a Cu reduction process and a dehydration process of the interlayer insulating film. In this case, the processing gas is supplied to the second insulating layer 206 and heated, so that the dehydration process of the second insulating layer 206 is promoted, and the electric power of the second insulating layer 206 is increased. Effects such as reduction of dielectric constant and improvement of withstand voltage are obtained.
[0051] このような脱水処理による電気特性の改善の効果は、例えば前記第 2の絶縁層 20 6が、シリコン酸化膜（SiO膜）の場合であっても得られるが、該第 2の絶縁層 206が  [0051] The effect of improving the electrical characteristics by such dehydration can be obtained, for example, even when the second insulating layer 206 is a silicon oxide film (SiO film). Layer 206
2  2
吸水性の大きい、 Low_k材料よりなる場合、特にその効果が大きくなる。このような 低誘電率材料 (低誘電率層間絶縁膜)の例としては、例えば、多孔質膜もしくはフッ 素を含む膜などがある。 The effect is particularly great when it is made of a low-k material with high water absorption. Examples of such a low dielectric constant material (low dielectric constant interlayer insulating film) include, for example, a porous film or a hook. There is a film containing element.
[0052] また、 Cuの酸化膜除去の処理を安定に、また効率よく行うためには、前記基板処 理装置 100Xを用いて、本工程において被処理基板上に H Oを供給するようにして  [0052] Further, in order to stably and efficiently perform the Cu oxide film removal process, the substrate processing apparatus 100X is used to supply H 2 O onto the substrate to be processed in this step.
2  2
もよレ、。また、この場合、層間絶縁膜の脱水効果を鑑みて、供給される H Oの量を適  Moyore. In this case, considering the dehydration effect of the interlayer insulating film, the amount of supplied H 2 O is appropriately adjusted.
2 宜制御することが好ましい。すなわち、層間絶縁膜の吸水性がより大きい場合、供給 される H〇の量を少なく（もしくは 0に）し、層間絶縁膜の吸水性が小さい場合は、 Cu 2 It is preferable to control appropriately. In other words, when the water absorption of the interlayer insulating film is larger, the amount of supplied H0 is reduced (or reduced to 0), and when the water absorption of the interlayer insulating film is small, Cu
2 2
の還元処理の安定を考慮して供給される H Oの量を多くすればよい。  The amount of H 2 O supplied should be increased in consideration of the stability of the reduction treatment.
2  2
[0053] また、本実施例で用いられる処理ガスである、有機酸アンモニゥム塩、有機酸ァミン 塩、有機酸アミド、および有機酸ヒドラジドを構成する有機酸は、例えばカルボン酸よ りなるものを用いることができる。  [0053] Further, as the processing gas used in this example, the organic acid constituting the organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is, for example, one made of carboxylic acid. be able to.
[0054] また、本実施例で用いられる処理ガスである、有機酸アンモニゥム塩、有機酸ァミン 塩は、 Rl _CO〇_NR2R3R4R5 (Rl， R2, R3， R4, R5は、水素原子もしくは炭 化水素基もしくは炭化水素基を構成する水素原子の少なくとも一部がハロゲン原子 に置換された官能基。）で示されるものである。具体的な炭化水素基としては、アルキ ル基、アルケニル基、アルキニル基、ァリール基などを挙げることができる。具体的な ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素を挙げること力 Sできる。  [0054] The processing gas used in this example is an organic acid ammonium salt or an organic acid amine salt. Rl_COO_NR2R3R4R5 A functional group in which at least a part of the hydrogen atoms constituting the group or hydrocarbon group are substituted with halogen atoms. Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Specific halogen atoms can include fluorine, chlorine, bromine and iodine.
[0055] また、有機酸アンモニゥム塩、有機酸ァミン塩の例としては、有機酸アンモニゥム（R 1COONH )、または、有機酸メチルァミン塩、有機酸ェチルァミン塩、有機酸 tーブ  [0055] Examples of the organic acid ammonium salt and organic acid amine salt include organic acid ammonium salt (R 1COONH), organic acid methylamine salt, organic acid ethylamine salt, organic acid tube.
4  Four
チルァミン塩などの一級アミン塩、または、有機酸ジメチルァミン塩、有機酸ェチルメ チルァミン塩、有機酸ジェチルァミン塩などの二級アミン塩、または、有機酸トリメチ ルァミン塩、有機酸ジェチルメチルァミン塩、有機酸ェチルジメチルァミン塩、有機酸 トリメチルァミン塩などの三級アミン塩、または、有機酸テトラメチルアンモニゥム、有 機酸トリェチルメチルアンモニゥムなどの四級アンモニゥム塩がある。  Primary amine salts such as tyramine salts, or secondary amine salts such as organic acid dimethylamine salts, organic acid ethylmethylamine salts, organic acid jetylamine salts, organic acid trimethylamine salts, organic acid jetylmethylamine salts, organic There are tertiary amine salts such as ethyldimethylamine salt and organic acid trimethylamine salt, or quaternary ammonium salts such as organic acid tetramethylammonium and organic acid triethylmethylammonium.
[0056] また、本実施例で用いられる処理ガスである、有機酸アミドは、 R6 -CO-NH2 (R 6は、水素原子もしくは炭化水素基もしくは炭化水素基を構成する水素原子の少なく とも一部がハロゲン原子に置換された官能基。）で示されるものである。具体的な炭 化水素基としては、アルキル基、アルケニル基、アルキニル基、ァリール基などを挙 げること力 Sできる。具体的なハロゲン原子としては、フッ素、塩素、臭素、ヨウ素を挙げ ること力 Sできる。例えば、有機酸アミドの例としては、カルボン酸アミド（RCONH )が [0056] Further, the organic acid amide that is a processing gas used in this example is R6 -CO-NH2 (R6 is a hydrogen atom, a hydrocarbon group, or a hydrogen atom constituting a hydrocarbon group. A functional group in which a part is substituted with a halogen atom.) Specific hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. Specific halogen atoms include fluorine, chlorine, bromine and iodine. Ability to do S. For example, as an example of organic acid amide, carboxylic acid amide (RCONH) is
2 ある。  There are two.
[0057] また、本実施例で用いられる処理ガスである、有機酸ヒドラジドは、 R7-CO-NH 0NH2 (R7は、水素原子もしくは炭化水素基もしくは炭化水素基を構成する水素原 子の少なくとも一部がハロゲン原子に置換された官能基。）で示されるものである。具 体的な炭化水素基としては、アルキル基、アルケニル基、アルキニル基、ァリール基 などを挙げること力 Sできる。具体的なハロゲン原子としては、フッ素、塩素、臭素、ヨウ 素を挙げることができる。  [0057] Further, the organic acid hydrazide, which is a processing gas used in this example, is R7-CO-NH0NH2 (R7 is at least one of hydrogen atoms constituting a hydrogen atom, a hydrocarbon group, or a hydrocarbon group. A functional group in which a part is substituted with a halogen atom.) Specific hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.
[0058] また、上記の有機酸の例としては、カルボン酸があり、例えば、酢酸、蟻酸、プロピ オン酸、酪酸、酢酸ギ酸、および吉草酸などがある。  [0058] Examples of the organic acid include carboxylic acids such as acetic acid, formic acid, propionic acid, butyric acid, acetic acid formic acid, and valeric acid.
[0059] 上記の図 3Cの工程において、例えば、処理ガスの流量は 1乃至 1000sccm、前記 処理空間 101Aの圧力は、 1乃至 lOOOPa、被処理基板の温度は、 100乃至 300°C 、処理時間は、 1乃至 180秒として、上記の処理を行うことができる。また、水蒸気を 用いる場合には、水蒸気の流量は、 1乃至 lOOOsccmとすることが好ましい。また、前 記反応促進室 102Bの温度は、被処理基板の温度より高いことが好ましい。  In the process shown in FIG. 3C, for example, the flow rate of the processing gas is 1 to 1000 sccm, the pressure of the processing space 101A is 1 to lOOOPa, the temperature of the substrate to be processed is 100 to 300 ° C., and the processing time is The above processing can be performed for 1 to 180 seconds. When water vapor is used, the flow rate of water vapor is preferably 1 to lOOOOsccm. In addition, the temperature of the reaction promoting chamber 102B is preferably higher than the temperature of the substrate to be processed.
[0060] 次に、図 3Dに示す工程において、前記溝部 207aおよび前記ホール部 207bの内 壁面を含む前記第 2の絶縁層 206上、および前記配線部 204の露出面に、 Cu拡散 防止膜 207cの成膜を行う。前記 Cu拡散防止膜 207cは、例えば高融点金属膜やこ れらの窒化膜、または高融点金属膜と窒化膜の積層膜力 なる。例えば当該 Cu拡 散防止膜 207cは、 Ta/TaN膜、 WN膜、または TiN膜などからなり、スパッタ法ゃ C VD法などの方法により、形成することが可能である。また、このような Cu拡散防止膜 は、いわゆる ALD法によって形成することも可能である。  Next, in the step shown in FIG. 3D, a Cu diffusion preventing film 207c is formed on the second insulating layer 206 including the inner wall surfaces of the groove portion 207a and the hole portion 207b and on the exposed surface of the wiring portion 204. The film is formed. The Cu diffusion preventing film 207c is, for example, a refractory metal film, a nitride film thereof, or a laminated film force of the refractory metal film and the nitride film. For example, the Cu diffusion prevention film 207c is made of a Ta / TaN film, a WN film, or a TiN film, and can be formed by a method such as sputtering or CVD. Such a Cu diffusion barrier film can also be formed by the so-called ALD method.
[0061] 次に図 3Eに示す工程において、前記溝部 207aおよび前記ホール部 207bを含む 、前記 Cu拡散防止膜 207cの上に、 Cuよりなる配線部 207を形成する。この場合、 例えばスパッタ法ゃ CVD法で Cuよりなるシード層を形成した後、 Cuの電界メツキに より、前記配線部 207を形成することができる。また、 CVD法や ALD法により、前記 配線部 207を形成してもよい。  Next, in a step shown in FIG. 3E, a wiring portion 207 made of Cu is formed on the Cu diffusion preventing film 207c including the groove portion 207a and the hole portion 207b. In this case, for example, after forming a seed layer made of Cu by sputtering or CVD, the wiring portion 207 can be formed by electric field measurement of Cu. Further, the wiring portion 207 may be formed by a CVD method or an ALD method.
[0062] 配線部 207を形成後、化学機械研磨（CMP)法により基板表面を平坦化する。 [0063] また、本工程の後に、さらに前記第 2の絶縁層の上部に第 2 + n (nは自然数）の絶 縁層を形成し、それぞれの絶縁層に上記の方法により Cuよりなる配線部を形成し、 多層配線構造を有する半導体装置を形成することが可能である。 [0062] After forming the wiring portion 207, the substrate surface is planarized by a chemical mechanical polishing (CMP) method. [0063] Further, after this step, a 2 + n insulating layer (n is a natural number) is further formed on the second insulating layer, and a wiring made of Cu is formed on each insulating layer by the above method. It is possible to form a semiconductor device having a multilayer wiring structure.
[0064] また、本実施例では、デュアルダマシン法を用いて、 Cuの多層配線構造を形成す る場合を例にとって説明した力 シングルダマシン法を用いて Cuの多層配線構造を 形成する場合にも上記の方法を適用できることは明らかである。  In this embodiment, the force described in the case of forming a Cu multilayer wiring structure using the dual damascene method as an example. Also in the case of forming a Cu multilayer wiring structure using the single damascene method. Obviously, the above method can be applied.
[0065] また、本実施例では、絶縁層に形成される金属配線として、おもに Cu配線を例にと つて説明したが、これに限定されるものではなレ、。例えば、 Cuのほ力に、 Ag， W， Co , Ru, Ti， Taなどの金属（配線）に対しても本実施例を適用することが可能である。  [0065] In the present embodiment, the Cu wiring is mainly described as an example of the metal wiring formed in the insulating layer. However, the present invention is not limited to this. For example, this embodiment can also be applied to metals (wirings) such as Ag, W, Co, Ru, Ti, Ta, etc. in addition to Cu.
[0066] また、本発明を実施可能な基板処理装置は、実施例 1または実施例 2で説明した 基板処理装置に限定されず、様々に変形 ·変更が可能である。例えば、図 4は、実施 例 1に記載した基板処理装置 100の変形例である、基板処理装置 100Yである。た だし図中、先に説明した部分には同一の参照符号を付し、説明を省略する。  Further, the substrate processing apparatus capable of implementing the present invention is not limited to the substrate processing apparatus described in the first embodiment or the second embodiment, and various modifications and changes can be made. For example, FIG. 4 shows a substrate processing apparatus 100Y that is a modification of the substrate processing apparatus 100 described in the first embodiment. However, in the figure, the same reference numerals are given to the parts described above, and the description is omitted.
[0067] 図 4を参照するに、前記基板処理装置 100Yでは、前記基板処理装置 100に設置 された前記原料供給手段 110に換わって、原料供給手段 310が設置されている。前 記原料供給手段 310は、いわゆるパブリング方式で前記原料 110aを気化もしくは昇 華させて前記ガス供給ライン 107より前記処理空間 101Aに供給することが可能に構 成されている。  Referring to FIG. 4, in the substrate processing apparatus 100Y, a raw material supply means 310 is installed in place of the raw material supply means 110 installed in the substrate processing apparatus 100. The raw material supply means 310 is configured to vaporize or sublimate the raw material 110a by a so-called publishing method and supply it to the processing space 101A from the gas supply line 107.
[0068] 前記原料供給手段 310には、ガスライン 311よりキャリアガスとして不活性ガス（たと えば Heなど）が供給され、気化もしくは昇華した原料は当該キャリアガスとともに処理 容器に供給される。  [0068] The raw material supply means 310 is supplied with an inert gas (for example, He) as a carrier gas from a gas line 311, and the vaporized or sublimated raw material is supplied to the processing vessel together with the carrier gas.
[0069] このように、本実施例による半導体装置の製造方法では、 Cuに形成される酸化膜 の除去を、金属汚染の影響を低減して、安定に効率よく行うことが可能であり、さらに Cuの酸化膜の除去と共に、層間絶縁膜の脱水処理を行うことが可能である。このた め、上記の方法では、従来は別々の工程で行っていた Cuの酸化膜除去と層間絶縁 層の脱水処理を実質的に同時に行うことが可能になり、半導体装置の製造工程が単 純となっている。  As described above, in the method of manufacturing the semiconductor device according to this example, the removal of the oxide film formed on Cu can be stably and efficiently performed while reducing the influence of metal contamination. Along with the removal of the Cu oxide film, the interlayer insulating film can be dehydrated. For this reason, the above-described method makes it possible to perform Cu oxide film removal and dehydration treatment of the interlayer insulating layer, which were conventionally performed in separate steps, at substantially the same time, thereby simplifying the semiconductor device manufacturing process. It has become.
[0070] また、上記の実施例では、金属層の酸化膜除去と層間絶縁層の脱水処理を同時 に行う例について説明している力 本発明はこれに限定されるものではなレ、。例えば 、実質的に金属層の酸化膜除去を行わずに、層間絶縁膜の脱水処理のみを単独で 行うことも可能である。この場合、処理ガスとして、上記の実施例中に記載した有機酸 アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジドを用いること が可能である。この場合、基板処理方法、および基板処理装置については、上記の 実施例中に記載した場合と同様の方法、装置を用いて同様に行うことが可能である。 [0070] In the above embodiment, the removal of the oxide film of the metal layer and the dehydration treatment of the interlayer insulating layer are performed simultaneously. The force explaining the example performed in the present invention is not limited to this. For example, it is possible to perform only the dehydration treatment of the interlayer insulating film alone without substantially removing the oxide film of the metal layer. In this case, the organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide described in the above-mentioned examples can be used as the processing gas. In this case, the substrate processing method and the substrate processing apparatus can be similarly performed using the same method and apparatus as those described in the above embodiments.
[0071] 以上、本発明を好ましい実施例について説明したが、本発明は上記の特定の実施 例に限定されるものではなく、特許請求の範囲に記載した要旨内におレ、て様々な変 形-変更が可能である。  The present invention has been described with reference to the preferred embodiments. However, the present invention is not limited to the specific embodiments described above, and various modifications can be made within the scope described in the claims. Shape-changeable.
[0072] 例えば、上記の実施例では、絶縁層に対してエッチングを行って形成された開口 部に露出した下層配線の Cu表面酸化膜を除去する工程に対して、本発明の基板処 理方法を適用しているが、他の工程で Cuの表面酸化膜を除去する場合に本発明を 適用してもよい。  [0072] For example, in the above embodiment, the substrate processing method of the present invention is applied to the step of removing the Cu surface oxide film of the lower layer wiring exposed in the opening formed by etching the insulating layer. However, the present invention may be applied to the case where the Cu surface oxide film is removed in another process.
[0073] 例えば、シード層あるいは配線層を形成した後、もしくは CMPを行った後に対して 本発明を適用してもよい。  [0073] For example, the present invention may be applied to a seed layer or a wiring layer after it is formed or after CMP.
産業上の利用可能性  Industrial applicability
[0074] 本発明によれば、半導体装置の製造工程において、金属配線に形成される酸化膜 を除去する場合の金属汚染の影響を低減することが可能となる。 According to the present invention, it is possible to reduce the influence of metal contamination when an oxide film formed on a metal wiring is removed in a semiconductor device manufacturing process.
[0075] 本国際出願は、 2006年 3月 27日に出願した日本国特許出願 2006— 086565号 に基づく優先権を主張するものであり、 2006— 086565号の全内容を本国際出願 に援用する。 [0075] This international application claims priority based on Japanese Patent Application No. 2006-086565 filed on Mar. 27, 2006. The entire contents of 2006-086565 are incorporated herein by reference. .

Claims

請求の範囲 The scope of the claims
[I] 絶縁膜と金属層が形成された、被処理基板の基板処理方法であって、  [I] A substrate processing method of a substrate to be processed, in which an insulating film and a metal layer are formed,
前記被処理基板上に、有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、およ び有機酸ヒドラジドのうち、少なくともいずれ力 4つを含む物質の蒸気を供給するとと もに前記被処理基板を加熱する処理工程を有することを特徴とする基板処理方法。  The substrate to be treated is supplied with vapor of a substance containing at least four of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide on the substrate to be treated. A substrate processing method comprising a processing step of heating the substrate.
[2] 前記金属層は、 Cuよりなることを特徴とする請求項 1記載の基板処理方法。  2. The substrate processing method according to claim 1, wherein the metal layer is made of Cu.
[3] 前記処理工程の前記被処理基板の温度が、 100°C乃至 300°Cであることを特徴と する請求項 2記載の基板処理方法。  3. The substrate processing method according to claim 2, wherein the temperature of the substrate to be processed in the processing step is 100 ° C. to 300 ° C.
[4] 前記処理工程では、前記金属層に形成された酸化膜が除去されることを特徴とす る請求項 1記載の基板処理方法。 4. The substrate processing method according to claim 1, wherein, in the processing step, an oxide film formed on the metal layer is removed.
[5] 前記処理工程では、前記絶縁膜の脱水処理が行われることを特徴とする請求項 4 記載の基板処理方法。 5. The substrate processing method according to claim 4, wherein in the processing step, the insulating film is dehydrated.
[6] 前記絶縁膜は、多孔質膜またはフッ素を含む膜のレ、ずれかを含むことを特徴とする 請求項 5記載の基板処理方法。  6. The substrate processing method according to claim 5, wherein the insulating film includes a gap between a porous film and a film containing fluorine.
[7] 前記処理工程では、前記被処理基板上に前記物質とともに H Oが供給されること [7] In the processing step, H 2 O is supplied together with the substance onto the substrate to be processed.
2  2
を特徴とする請求項 1記載の基板処理方法。  The substrate processing method according to claim 1, wherein:
[8] 前記有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジ ドを構成する有機酸は、カルボン酸であることを特徴とする請求項 1記載の基板処理 方法。 8. The substrate processing method according to claim 1, wherein the organic acid constituting the organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is a carboxylic acid.
[9] 金属配線と層間絶縁膜を含む、半導体装置の製造方法であって、  [9] A method for manufacturing a semiconductor device, including a metal wiring and an interlayer insulating film,
前記金属配線と前記層間絶縁膜が形成された被処理基板上に、有機酸アンモニ ゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジドのうち、少なくともいず れか 1つを含む物質の蒸気を供給すると共に前記被処理基板を加熱する処理工程 を含むことを特徴とする半導体装置の製造方法。  A substrate to be processed on which the metal wiring and the interlayer insulating film are formed includes at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide. A method of manufacturing a semiconductor device, comprising: a processing step of supplying a vapor of a substance and heating the substrate to be processed.
[10] 前記金属配線は、 Cuよりなることを特徴とする請求項 9記載の半導体装置の製造 方法。 10. The method for manufacturing a semiconductor device according to claim 9, wherein the metal wiring is made of Cu.
[II] 前記処理工程の前記被処理基板の温度が、 100°C乃至 300°Cであることを特徴と する請求項 10記載の半導体装置の製造方法。 [II] The method of manufacturing a semiconductor device according to claim 10, wherein the temperature of the substrate to be processed in the processing step is 100 ° C. to 300 ° C.
[12] 前記処理工程では、前記金属配線に形成された酸化膜が除去されることを特徴と する請求項 9記載の半導体装置の半導体装置の製造方法。 12. The method for manufacturing a semiconductor device of a semiconductor device according to claim 9, wherein, in the processing step, an oxide film formed on the metal wiring is removed.
[13] 前記処理工程では、前記層間絶縁膜の脱水処理が行われることを特徴とする請求 項 12記載の半導体装置の半導体装置の製造方法。 13. The method for manufacturing a semiconductor device of a semiconductor device according to claim 12, wherein in the processing step, dehydration processing of the interlayer insulating film is performed.
[14] 前記層間絶縁膜は、多孔質膜またはフッ素を含む膜のいずれ力 ^含むことを特徴 とする請求項 13記載の半導体装置の製造方法。 14. The method of manufacturing a semiconductor device according to claim 13, wherein the interlayer insulating film includes any force of a porous film or a film containing fluorine.
[15] 前記処理工程では、前記被処理基板上に前記物質とともに H Oが供給されること [15] In the processing step, H 2 O is supplied together with the substance onto the substrate to be processed.
2  2
を特徴とする請求項 9記載の半導体装置の製造方法。  The method for manufacturing a semiconductor device according to claim 9.
[16] 前記有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有機酸ヒドラジ ドを構成する有機酸は、カルボン酸であることを特徴とする請求項 9記載の半導体装 置の製造方法。 16. The method for producing a semiconductor device according to claim 9, wherein the organic acid constituting the organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is a carboxylic acid. .
[17] 被処理基板を保持すると共に該被処理基板を加熱する保持台と、  [17] A holding table for holding the substrate to be processed and heating the substrate to be processed;
前記保持台を内部に備えた処理容器と、  A processing container having the holding table therein;
前記処理容器内に、処理ガスを供給するガス供給部と、を備えた基板処理装置で あってヽ  A substrate processing apparatus comprising: a gas supply unit configured to supply a processing gas in the processing container.
前記処理ガスは、有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、および有 機酸ヒドラジドのうち、少なくともいずれ力 1つを含むことを特徴とする基板処理装置。  The substrate processing apparatus, wherein the processing gas includes at least one of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide.
[18] 前記被処理基板には、金属層と絶縁膜が形成されていることを特徴とする請求項 1[18] The metal substrate and the insulating film are formed on the substrate to be processed.
7記載の基板処理装置。 7. The substrate processing apparatus according to 7.
[19] 前記処理容器内に前記処理ガスが供給されることにより、前記金属層に形成された 酸化膜が除去されることを特徴とする請求項 18記載の基板処理装置。 19. The substrate processing apparatus according to claim 18, wherein an oxide film formed on the metal layer is removed by supplying the processing gas into the processing container.
[20] 前記処理容器内に前記処理ガスが供給されることにより、前記絶縁膜の脱水処理 がおこなわれることを特徴とする請求項 19記載の基板処理装置。 20. The substrate processing apparatus according to claim 19, wherein the insulating film is dehydrated by supplying the processing gas into the processing container.
[21] 前記処理容器内に H〇を供給する H〇供給手段をさらに有することを特徴とする [21] The apparatus further comprises HO supply means for supplying HO into the processing container.
2 2  twenty two
請求項 17記載の基板処理装置。  The substrate processing apparatus according to claim 17.
[22] 前記 H O供給手段は、水蒸気発生器を含むことを特徴とする請求項 21記載の基 [22] The base according to [21], wherein the H 2 O supply means includes a water vapor generator.
2  2
板処理装置。  Plate processing equipment.
[23] 被処理基板を保持すると共に該被処理基板を加熱する保持台と、 前記保持台を内部に備えた処理容器と、 [23] a holding table for holding the substrate to be processed and heating the substrate to be processed; A processing container having the holding table therein;
前記処理容器内に、処理ガスを供給するガス供給部と、を備えた基板処理装置に よる基板処理方法を、コンピュータによって動作させるプログラムを記憶した記録媒 体であって、  A recording medium storing a program for operating a substrate processing method by a substrate processing apparatus provided with a gas supply unit for supplying a processing gas in the processing container by a computer,
前記基板処理方法は、  The substrate processing method includes:
前記被処理基板上に、有機酸アンモニゥム塩、有機酸ァミン塩、有機酸アミド、およ び有機酸ヒドラジドのうち、少なくともいずれ力 4つを含む物質を含む前記処理ガスを 供給するとともに前記被処理基板を加熱する処理工程を有することを特徴とする記 録媒体。  The processing gas containing a substance containing at least four of organic acid ammonium salt, organic acid amine salt, organic acid amide, and organic acid hydrazide is supplied to the substrate to be processed and the substrate to be processed. A recording medium comprising a processing step of heating a substrate.
PCT/JP2007/054975 2006-03-27 2007-03-13 Method of substrate treatment, process for producing semiconductor device, substrate treating apparatus, and recording medium WO2007111126A1 (en)

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